Formation and strain distribution of Ni/NiO core/shell magnetic nanoparticles fabricated by pulsed laser deposition

Nucleation and growth lead to substantial strain in nanoparticles embedded in a host matrix.The distribution of strain field plays an important role in the physical properties of nanoparticles.Magnetic Ni/NiO core/shell nanoparticles embedded in the amorphous Al2O3 matrix were fabricated by pulsed laser deposition.The results from a high-resolution transmission electron microscope also revealed that the core/shell nanoparticles consist of a single crystal Ni core with a faced-centered cubic structure(Space ...     

Chemical synthesis of self-assembled Ni nanoparticles and understanding of nonmagnetic layer inside their surface

To chemically synthesize mono-dispersed and self-assembled Ni nanoparticles, it was important to find the best combination of a Ni precursor and a ligand. Our Ni nanoparticles exhibited a face-centered cubic structure and superparamagnetism at room temperature. The value of saturation magnetization for our Ni nanoparticles was largely different from that of bulk Ni. Because of the relationship between the diameter and saturation magnetization per volume, the number of atoms composing the Ni nanoparticle was correlated with magnetization. This result indicated that a magnetic core/shell structure inside a Ni nanoparticle was produced. The nonmagnetic layer, as a magnetic shell of the core/shell structure, was created due to the low crystallinity of Ni nanoparticles and was composed of amorphous Ni‒O states. As a result, antiferromagnetic spins arrayed in the Ni‒O states were broken. Disordered spins were generated, which eventually decreased the total magnetization of the Ni nanoparticles.     

A novel two-phase thermal approach for synthesizing CdSe/CdS core/shell nanostructure

CdSe/CdS core/shell nanocrystals have been synthesized through a low cost and simple two-phase thermal route. The optical spectroscopy and structural characterization evidenced the core/shell structure of the CdSe/CdS nanoparticles. The X-ray diffraction patterns of CdSe and CdSe/CdS nanoparticles exhibited peak positions corresponding to those of their bulk cubic crystal structures. The X-ray photoelectron spectroscopy data confirmed the elemental composition of the CdSe/CdS nanoparticles. The absorption spectra of core/shell nanoparticles showed red shift with respect to the core CdSe nanoparticles. The photoluminescence study indicates that the intensity of the emission maximum is considerably increased in the core/shell structure as compared with the parent material, and the capping of CdS nanoparticles with CdSe material exhibit a near band-edge emission, indicating a successful passivation by removing surface defects. The high-resolution transmission microscope images of the bare and core/shell nanoparticles ascertained the monodispersed and well-defined spherical particles. The average particle sizes for CdSe and CdSe/CdS nanoparticles are 2.5 and 5 nm, respectively, thus confirming, the larger diameter of CdSe/CdS core/shell nanostructure than the core CdSe nanoparticles.     

Pt-Au核-壳结构纳米粒子热稳定性的分子动力学研究

采用分子动力学方法结合嵌入原子势, 对Pt-Au核-壳纳米粒子的热稳定性进行了研究. 计算结果表明: Pt-Au纳米粒子的熔点明显高于Au纳米粒子而低于Pt纳米粒子. 通过计算Lindemann指数发现: 壳层中的Au首先熔化, 然后逐渐向内部扩展, 最终导致核中的Pt完全熔化; 熔化所经历的温度区间明显宽于单质纳米粒子, 而且该熔化过程呈现典型的两阶段熔化特征; 在两次熔化之间, 存在着固(核)液(壳)共存的结构. 关键词： 纳米粒子 熔化 分子动力学     

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morié pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going. Received 29 November 2000     

银/二氧化钛核壳纳米颗粒对碲化镉纳米晶的荧光增强研究

利用新合成的复合纳米结构银/二氧化钛核壳纳米颗粒,研究了金属银纳米颗粒对碲化镉纳米晶层荧光的增强情况.结果表明,这种新型复合金属纳米结构能极大地增强发光纳米晶层的荧光强度.银/二氧化钛核壳纳米颗粒是以水合肼、硝酸银和四异丙氧基钛为原材料,利用胶体化学法在水溶液中合成.透射电子显微镜图片表明这种新合成的银/二氧化钛纳米材料基本上呈球形,有较为明显的核壳结构,中间黑色的核是银纳米颗粒,外层颜色较浅部分是二氧化钛壳层.另外,包裹二氧化钛壳层后,银纳米颗粒的表面等离子吸收带从409 nm红移至430 nm,也证实了这种新型核壳纳米材料的形成.将此合成方法得到的银/二氧化钛纳米颗粒和碲化镉纳米晶用旋转涂覆方法进行直接组合后,得到了银纳米颗粒对碲化镉纳米晶荧光的明显增强,并对其增强的物理过程进行了讨论.这种能够增强荧光团发光的新型复合银纳米结构将在发光器件、荧光成像、生物探测等方面具有一定的应用价值.     

Microstructure characterization and magnetic properties of nanomaterials

The microstructure and superparamagnetic properties of two systems of magnetic nano-particles are reviewed. A new type of magnetic core-shell Ni—Ce nanocomposite particle (15–50 nm) has been prepared. Typical HREM images and FFT patterns of HREM images showed that many planar defects (nanotwins and stacking faults) exist in the large Ni core zone (10–45 nm). The shell layers (3–5 nm) consist of an innermost Ni—Ce alloy and an outermost NiO oxide. FFT patterns from different regions of typical HREM images show well defined spots characteristic of core-shell nanocomposite materials. Magnetization measurements as a function of magnetic field and temperature showed that superparamagnetic behaviour is exhibited above the average block temperature (T_B = 170 K). This superpara-magnetic relaxation was found to be modified by interparticle interactions that depend on the applied field and size distribution. In addition, antiferromagnetic order occurred with a Neél temperature T_N of about 11 K. A spin-flip transition was observed below T_N at a certain applied field. Novel carbon encapsulated Ni nanoparticles assemblies have been synthesized by modified arc-discharge under a methane atmosphere. The presence of carbon encapsulation is confirmed by HR-TEM lattice imaging, and nanodiffraction. The intimate and contiguous carbon fringe around these Ni nanoparticles is good evidence for complete encapsulation by carbon shell layers. Superparamagnetic property studies show that the blocking temperature T_B is around 115K at 0.1 T applied field. Above T_B, the magnetization M(H,T) can be described by the classical Langevin function L using the relation M/M_s(T = 0) = coth (μH/kT) — kT/μH. The particle size can be inferred from the Langevin fit (particle moment μ), which is a little larger than the HR-TEM observation. It is suggested that these assemblies of carbon encapsulated Ni nanoparticles have typical single-domain, field-dependent superparamagnetic relaxation properties, and this typical superparamagnetic behaviour is consistent with the Stoner—Wohlfarth theory of single-domain particles.     

Synthesis and Structure of Magnetic Core-shell Ni–Ce Nanocomposite Particles

A new type of magnetic core-shell Ni–Ce nanocomposite particles (15–50 nm) is presented. SEM observations suggest the particles are strongly ferromagnetic, interacting with ordered chain-like features. Typical HR-TEM images demonstrate that many planar defects (nanotwins and stacking faults) exist in the surface shell and large Ni core zone (10–40 nm) of the particles; the inner shell layers (4–6 nm) consist of NiCe alloy and the outermost shell is NiO. Nano-diffraction patterns show an indication of well-defined spots characteristic of nanocomposite materials, of which certain crystal facet orientation relationships between orthorhombic [111] of NiCe and cubic [311] of Ni₂Ce, face-center crystal [222] of NiO, cubic [111] of nickel have been identified. This confirms the nature of this core-shell nanocomposite particle.     

Electrical properties of composites based on polystyrene with hybrid silicon dioxide particles

Composites based on polysterene and hybrid core-shell nanoparticles are studied; the nanoparticle core consists of silicon dioxide, and ethylphenylic groups (organic shell) are grafted to the core surface. It is shown that the permittivity, the volume resistivity, the thermostimulated depolarization current spectra, and the glass transition temperature of these materials depend on the nanofiller content and, what is more important, the nanofiller distribution over the polymer volume in the form of particles or their aggregates.     

Structural and thermal stabilities of Au@Ag core-shell nanoparticles and their arrays:A molecular dynamics simulation

Thermal stability of core-shell nanoparticles(CSNPs)is crucial to their fabrication processes,chemical and physical properties,and applications.Here we systematically investigate the structural and thermal stabilities of single Au@Ag CSNPs with different sizes and their arrays by means of all-atom molecular dynamics simulations.The formation energies of all Au@Ag CSNPs we reported are all negative,indicating that Au@Ag CSNPs are energetically favorable to be formed.For Au@Ag CSNPs with the same core size,their melting points increase with increasing shell thickness.If we keep the shell thickness unchanged,the melting points increase as the core sizes increase except for the CSNP with the smallest core size and a bilayer Ag shell.The melting points of Au@Ag CSNPs show a feature of non-monotonicity with increasing core size at a fixed NP size.Further simulations on the Au@Ag CSNP arrays with 923 atoms reveal that their melting points decrease dramatically compared with single Au@Ag CSNPs.We find that the premelting processes start from the surface region for both the single NPs and their arrays.     

First Observation of a Composition-Controlled Low-Moment/High-Moment Transition in the Fcc Fe-Ni System: Implications Regarding Invar and Anti-Invar Behaviors

We report the first direct observation of a high-moment (HM)/low-moment (LM) transition occurring in face centered cubic (FCC) Fe-Ni alloys. 57 Fe Mössbauer isomer shifts (ISs) give local electronic densities that exhibit a large discontinuity of , 0.4 el./ $ a_{0}^3 $ at the transition that spans the concentration range ～ 65-75 apc (atomic percent) Fe, in agreement with ab initio predictions. In the most Fe-rich alloys that have LM ground states (including n -Fe), we show that thermal stabilization of the HM state occurs at high temperatures, thereby providing an experimental proof that anti-Invar behavior is due to such HM stabilization. In Invar (Fe 65 Ni 35 ) and at near-Invar compositions, we observe temperature-induced changes in electronic density that follow the spontaneous magnetization curves and find that Invar is predominantly a HM phase at all temperatures where an Invar effect occurs. We show that LM phase thermal excitation cannot cause the Invar effect and that such excitation would cause a contraction instead of the required expansion, relative to normal behavior.     

Acoustic cavitation for engineering of gold sols in silver nitrate solutions

Binary gold-silver nanostructures of preformed gold nanoparticles (25nm) in silver nitrate solutions are produced by a two step sonication (20kHz). Ultrasonic treatment of gold-silver mixtures is carried out in the presence of sodium dodecyl sulfate in water or 2-propanol, and poly(vinyl pyrrolidone) in ethylene glycol solutions. Gold-silver nano-worms, which consist of ripened gold particles connected by ultrasonically reduced silver, are formed after 1h of sonication in the presence of sodium dodecyl sulfate aqueous solution. In 2-propanol bimetallic nano-worms have a well defined core-shell structure. Polygonal alloy nanoparticles with gold as a core material and a silver shell are produced after 180min of sonication in the presence of poly(vinyl pyrrolidone) in ethylene glycol solution. Bimetallic gold-silver nanostructures have defected face centered cubic structure and represent polycrystals with a large number of crystallites randomly oriented. For the first time, the mechanism of gold particle design by ultrasound is examined in detail. The role of additives (sodium dodecyl sulfate, polyvinyl pyrrolidone, ethylene glycol and 2-propanol) as reductants of silver at the gold contact surface or stabilizers of particles is highlighted.     

Characterization of semiconductor core-shell nanoparticles by resonant Raman scattering and photoluminescence spectroscopy

Colloidal CdSe nanoparticles (NPs), passivated with CdS and ZnS, were characterized by resonant Raman scattering and photoluminescence (PL). The effect of the passivating shell, its volume and formation procedure on optical and vibrational spectra is discussed. Analyzing the Raman peaks due to optical phonons inside the core and those related to the core-shell interface allows some understanding of the relation between the core-shell structure and its PL properties to be achieved. In particular, a compositional intermixing at the core/shell interface of the NPs was deduced from the Raman spectra, which can noticeably affect their PL intensity.     

Tuning the optical properties of Fe-Au core-shell nanoparticles with spherical and spheroidal nanostructures

Present research interest is to highlight on the manufacturing of core-shell nanoparticles because of core activity with unique properties and surface modification by a shell in the diverse fields (e.g. optoelectronic, catalysis and magneto-optics). In addition, the combined optical properties of magnetic-plasmonic core-shell NPs make them ideal candidates for many applications in biomedical fields. The influence of Fe-core and Au-shell for the formation of the core-shell viz. spherical and spheroidal nanostructures is studied using the discrete dipole approximation method. DDA is an approximation method and its accuracy is compared to Mie theory results for spherical core-shell NPs as Mie theory gives the exact solution to spherical targeted NPs. DDA calculations are further extended to spheroidal core-shell nanostructures. It is observed that the localized surface plasmon resonance (LSPR) peak position in considered core-shell nanostructures is enhanced by changing the cores and shell thickness in the core-shell spherical nanostructures and aspect ratio as well as shell thickness in spheroidal core-shell nanostructures. The absorption spectra are found between 363–788 nm wavelength ranges and can be tuned into UV-visible-near-infrared region of the electromagnetic (EM) spectrum in accordance with desired applications. It has been found that the Fe@hollow@Au and prolate core-shell nanostructures show enhancement to LSPR peaks, bandwidth and their corresponding intensities in comparison to other considered spherical and spheroidal core-shell nanostructures. Tunability in core size, shell thickness, aspect ratio, and configuration will open new potential uses of suitable magnetic-plasmonic core-shell nanostructures in cancer therapy, tissue engineering, drug delivery, and many more of biomedical fields.     

Theoretical investigation on near-infrared and visible absorption spectra of nanometallic aluminium with oxide coating in nanoenergetic materials: size and shape effects

The effects of metal core dimension, oxide shell thickness and ellipsoid aspect ratio of Al-Al2O3 core-shell nanoparticles on the near-infrared and visible absorption spectra of nanocomposite Al-Al2O3/nitrocellulose（NC） film are investigated by numerical calculations. Both the size-dependent interband transitions and frequency-dependent free electron damping of the nanometallic aluminium are taken into account in the calculations. Oxidation effect of nanoaluminium is also analysed. It is shown that oxidation may enhance but may also reduce the optical absorption, depending on the excited light energy and initial dimension of nanoparticle. Metal core size and excited light energy dominate the absorption characteristic. The absorption ability of ellipsoidal nanoparticles is larger than that of spheroidal nanoparticles and increases by the square index as the aspect ratio increases. These calculations will provide some significant theoretical guidance for the preparation and laser ignition of nanoenergetic materials.     

Morphological control of Ni/NiO core/shell nanoparticles and production of hollow NiO nanostructures

Chemical synthesis coupled with a microwave irradiation process allowed for the control of size (6–40 nm), shape, and shell thickness of Ni/NiO core/shell nanoparticles. In this unique synthetic route, the size of Ni nanoparticles (NiNPs) was strongly influenced by the nickel salt-to-stabilizer ratio and the amount of the stabilizer. Interestingly, it was observed that the shape of the nanoparticles was altered by varying the reaction time, where longer reaction times resulted in annealing effects and rupture of the stabilizer micelle leading to distinct shapes of Ni/NiO core/shell nanostructures. Product cooling rate was another important parameter identified in this study that not only affected the shape, but also the crystal structure of the core/shell nanoparticles. In addition, a simple and cost-effective method of microwave irradiation of NiNPs led to the formation of distinctly shaped hollow NiO nanoparticles. These high surface area core/shell nanoparticles with well-controlled morphologies are important and can lead to significant advancement in the design of improved fuel cells, electrochromic display devices, and catalysis systems.     

水热法促进EuVO_4@YVO_4核壳结构纳米颗粒中Eu~(3+)的扩散及其对发光性能的影响

采用共沉淀法制备了EuVO4@YVO4核壳结构纳米颗粒,然后用聚电解质聚苯乙烯磺酸钠对其进行包覆和保护,并在200?C下对样品水热处理0—48 h.在水热处理48 h后,样品的发光强度增强了约5倍,平均发光寿命由0.410 ms延长至0.579 ms.对样品的发光衰减曲线的拟合、分析为Eu3+的扩散提供了有力的证据.这种自内而外的扩散降低了样品核心中Eu3+的局域浓度,削弱了浓度猝灭效应,同时又能够避免表面猝灭效应的发生,从而使得样品的发光寿命变长、发光效率迅速提升.     

疏水基团修饰的核-壳型NaYF_4/NaLuF_4∶Yb~(3+),Tm~(3+)纳米粒子设计制备

通过异质核诱导,利用溶剂热法在较低温度下合成了具有疏水表面的上转换发光稀土核-壳Na YF4/Na Lu F4∶20%Yb,1%Tm纳米粒子,并利用X射线衍射仪、透射电子显微镜、傅里叶变换红外吸收光谱仪以及荧光光谱仪等测试设备对其进行了结构、形貌和上转换光谱的表征。测试结果表明,纳米粒子核为立方相,壳层为六角相。核-壳型纳米粒子的尺寸平均在20 nm以下,分布较为均匀。在980 nm近红外光激发下,核-壳型纳米粒子发射出较强的紫色和紫外荧光,且发光强度明显高于同尺寸立方相Na Lu F4∶20%Yb,1%Tm纳米粒子。这表明利用异质核诱导的方法制备的核-壳型纳米粒子在生物医学领域具有更高的应用价值。     

Role of the chemical ordering on the magnetic properties of Fe–Ni cluster alloys

The spin and orbital moments of fcc Fe-Ni cluster alloys are determined within the framework of a d-band Hamiltonian including the spin-orbit coupling non perturbatively. Different sizes (up to 321 atoms), compositions, and chemical configurations (random alloys as well as core-shell arrays of iron and nickel atoms) are considered in order to reveal the crucial role played by local order and stoichiometry on the magnetic moments of the clusters. Interestingly, we have found considerably reduced average magnetizations for Fe-Ni clusters with Fe cores compared to that of the bulk alloy with the same composition. Indeed, in these configurations not only antiparallel arrangements between the local moments of some Fe atoms within the iron core are found, but also the total magnetization of the surface Ni atoms is significantly quenched. On the opposite, the disordered and Ni-core cluster alloys are characterized by high magnetizations resulting from saturated-like contributions from both Ni and Fe atoms, in agreement with recent ab-initio calculations. In general, the local orbital magnetic moments are strongly enhanced with respect to their bulk values. Finally, the variation of the orbital-to-spin moment ratio with the chemical order is discussed.     

Growth of three-shell onionlike bimetallic nanoparticles

We show by molecular dynamics simulations on three systems (B/A=Pd/Ag, Cu/Ag, and Ni/Ag) that three-shell metallic nanoparticles made by a core of a metal A, an intermediate shell of metal B and an external shell of metal A (A-B-A nanoparticles) can be grown by deposition of B atoms onto an A core. The growth of the intermediate B shell is triggered by the fact that the most favorable positions for isolated B impurities inside A clusters are located just one layer below the cluster surface.